EP1013610A1 - Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre - Google Patents

Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre Download PDF

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EP1013610A1
EP1013610A1 EP99921191A EP99921191A EP1013610A1 EP 1013610 A1 EP1013610 A1 EP 1013610A1 EP 99921191 A EP99921191 A EP 99921191A EP 99921191 A EP99921191 A EP 99921191A EP 1013610 A1 EP1013610 A1 EP 1013610A1
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carbonate
nickel
droplets
hydroxide
emulsion
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EP1013610A4 (fr
EP1013610B1 (fr
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Kazuhiko Nagano
Kazunobu Abe
Shigefumi Kamisaka
Kiyoshi Fukai
Tsutoma Hatanaka
Shinji Ohgama
Hiroshi Nakao
Minoru Yoneda
Hideto Mizutani
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Sakai Chemical Industry Co Ltd
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Sakai Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/06—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/026—Spray drying of solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/90—Stabilisation; Use of additives

Definitions

  • M represents Ni, Co or Cu
  • a carbonate or a hydroxide of nickel, cobalt or copper is used as a starting material, and the carbonate herein the invention includes a normal carbonate (MCO 3 ) and a basic carbonate (xMO ⁇ yCO 2 ⁇ zH 2 O).
  • the carbonate may contain hydroxides.
  • the letter M represents nickel, cobalt or copper, as mentioned above.
  • the product obtained depends on the reaction conditions used. More specifically, when a hydroxide is dissolved in an aqueous solution containing ammonium carbonate, ammonium hydrogencarbonate or, a carbonate or a hydrogencarbonate (or bicarbonate) of an alkali metal (hereunder referred to as a (hydrogen) carbonate for simplicity), the resulting product is the corresponding carbonate. However, when a hydroxide is dissolved in aqueous ammonia which contains no (hydrogen)carbonate, the resulting product is the same hydroxide as the starting material.
  • the carbonate or hydroxide of nickel, cobalt or copper used as a starting material may be produced in any method.
  • a carbonate may be produced by neutralizing an inorganic salt such as a chloride, a sulfate, a nitrate or an organic acid salt such as an acetate with an alkali carbonate which contains carbonate ions such as sodium carbonate or ammonium carbonate.
  • An aqueous ammonia solution in which a carbonate or a hydroxide of nickel, cobalt or copper is dissolved therein may be prepared by dissolving an inorganic salt of the element such as a chloride, a sulfate, a nitrate or an organic acid salt of the element such as an acetate, or by reacting such salts with ammonia.
  • aqueous ammonia used in which the starting material, or a carbonate or a hydroxide of nickel, cobalt or copper, is dissolved contains a basic compound (other than ammonia) in addition to ammonia, the basic compound other than ammonia being referred to as the second basic compound.
  • the second basic compound is at least one of the (hydrogen) carbonates (i.e., ammonium carbonates, ammonium hydrogencarbonates, alkali metal carbonates and alkali metal hydrogencarbonates), alkali metal hydroxides and organic amines.
  • the above-mentioned alkali metal is preferably, for example, lithium, potassium or sodium.
  • the alkali metal carbonate, alkali metal hydrogencarbonate or alkali metal hydroxide may be exemplified by, for example, lithium carbonate, lithium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, lithium hydroxide, potassium hydroxide or sodium hydroxide.
  • the organic amine usable includes, for example, mono-, di- or trialkylamines, or mono-, di- or trialkanolamines, although the organic amines usable are not limited to these examples.
  • ammonium hydrogencarbonate is most preferred.
  • nickel carbonate is dissolved in aqueous ammonia containing a second basic compound, and the resulting solution is converted to a W/O emulsion containing droplets of the solution in a non-aqueous medium.
  • the droplets contain the nickel salt therein.
  • nickel carbonate is precipitated in the droplets by removing volatile components including ammonia (mainly composed of ammonia and carbon dioxide) from within the droplets. If necessary, a further volatile component mainly composed of water is removed from within the droplets to dry the nickel carbonate in the emulsion.
  • the thus formed nickel carbonate is separated by, for example, centrifugation, washed and dried to provide desired fine spherical particles of nickel carbonate.
  • nickel carbonate used as a starting material
  • the description is also applicable to cobalt carbonate, copper carbonate, nickel hydroxide, cobalt hydroxide and copper hydroxide.
  • nickel carbonate is dissolved in an aqueous ammonia solution at a pH in the range of 8.0 to 11.5, although not limited thereto.
  • a pH in the range of 8.0 to 11.5 it is easy to adjust the pH of the aqueous solution in which nickel carbonate is dissolved by using a second basic compound as mentioned hereinbefore together with ammonia as a basic material, especially by using a (hydrogen)carbonate.
  • aqueous solution of the nickel salt is then mixed with a non-aqueous medium and stirred in the presence of a surfactant to prepare an emulsion in a conventional manner per se well known. It is preferred that a more hydrophilic surfactant is added to the aqueous solution of the nickel salt and, if necessary, the solution is heated to a temperature less than 50°C so that ammonia does not evaporate and the surfactant is dissolved in the solution.
  • uniform, fine and spherical particles of carbonate or hydroxide of nickel, cobalt or copper are obtained by controlling or adjusting the average particle size and particle size distribution of the water phase (droplets) in the emulsion.
  • the non-aqueous medium in which the emulsion is prepared is preferably water-insoluble and, not volatile or only slightly volatile and, thus stable when being treated under a reduced or the normal pressure mentioned hereafter. Accordingly, for example, a non-aqueous medium that has a solubility in water is not more than 5% and has a boiling point higher than that of water is preferred.
  • non-aqueous media usable in the invention, natural oils such as mineral oil or, animal or vegetable oils, and synthetic oils such as hydrocarbon oil, ester oil, ether oil, fluorine-containing lubricant, phosphorus fluorine-containing lubricant or silicon-lubricant.
  • natural oils such as mineral oil or, animal or vegetable oils
  • synthetic oils such as hydrocarbon oil, ester oil, ether oil, fluorine-containing lubricant, phosphorus fluorine-containing lubricant or silicon-lubricant.
  • a hydrocarbon solvent which is water-insoluble and has a small vaporization pressure is preferably used as a non-aqueous medium, such as, for example, an aliphatic hydrocarbon solvent having a boiling point of not less than 100°C under the normal pressure.
  • the surfactant used for preparing an emulsion is chosen depending on the individual non-aqueous medium used.
  • a stable W/O emulsion may be prepared as follows.
  • a hydrophilic surfactant having a hydrophile-lypophile balance (HLB) value of not less than 10 is dissolved in the aqueous solution (water phase) of the nickel salt while a lypophilic surfactant having an HLB value of not more than 10 is dissolved in the non-aqueous medium (oil phase), and the water phase and oil phase are mixed together in order to obtain a stable emulsion.
  • HLB hydrophile-lypophile balance
  • the amount of surfactant used is determined depending on a water/oil ratio (W/O ratio) employed and a desired particle size of the droplets in the resulting emulsion. Although not limited, it is not more than 20% by weight, preferably in the range of 5 to 15% by weight, based on the weight of the emulsion.
  • a first surfactant is dissolved in the water phase in an amount of not more than 20% by weight, preferably in an amount of 0.5 to 15% by weight, based on the amount of the water phase while a second surfactant is dissolved in the oil phase in an amount of not more than 20% by weight, preferably in an amount of 0.5 to 15% by weight, based on the amount of the oil phase.
  • Nonionic surfactants having an HLB value of not less than 10 used for the preparation of emulsion include, for example, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolpalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate or polyoxyethylene sorbitan trioleate, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate or polyethylene glycol monooleate, polyoxyethylene higher alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether or polyoxyethylene oleyl ether, polyoxyethylene higher alkyl aryl ethers such as polyoxyethylene octylphenyl oleyl ether or polyoxyethylene nonylphenyl
  • Nonionic surfactants having an HLB value of not more than 10 used for the preparation of emulsion include, for example, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate or sorbitan trioleate, and glycerin fatty acid esters such as glycerin monostearate or glycerin monooleate.
  • fine spherical particles of nickel carbonate is obtained. That is, nickel carbonate or nickel hydroxide is dissolved in aqueous ammonia containing a (hydrogen)carbonate and the resulting solution of the nickel salt is dispersed in the form of droplets of the solution in a non-aqueous medium to prepare a W/O emulsion. The emulsion is then subjected to stirred or aerated under the normal pressure, if necessary with heating, or suction is applied to the emulsion under a reduced pressure, to evaporate volatile components mainly comprising ammonia and carbon dioxide from within the droplets, thereby to precipitate the nickel salt in the droplets in the emulsion.
  • nickel salt is then evaporated from within the droplets to dry the nickel salt in the emulsion.
  • the thus obtained nickel salt is then separated by, for example, centrifugation, washed and dried to provide the desired fine particles of nickel carbonate. This is also the case with cobalt carbonate, cobalt hydroxide, copper carbonate or copper hydroxide.
  • the thus formed spherical precipitates are separated by a suitable means, for example, by centrifugation or filtration, washed and dried, thereby providing the desired fine particles of nickel carbonate.
  • a suitable means for example, by centrifugation or filtration, washed and dried, thereby providing the desired fine particles of nickel carbonate.
  • cobalt carbonate, cobalt hydroxide, copper carbonate or copper hydroxide is also the case with cobalt carbonate, cobalt hydroxide, copper carbonate or copper hydroxide.
  • nickel hydroxide is dissolved in aqueous ammonia containing no (hydrogen)carbonate therein and the resulting solution is dispersed in the form of droplets of the solution in a non-aqueous medium to prepare a W/O emulsion.
  • the emulsion is then stirred or aerated under the normal pressure, if necessary with heating, or suction is applied to the emulsion under a reduced pressure, to evaporate volatile components mainly comprising ammonia and carbon dioxide from within the droplets, thereby to precipitate nickel hydroxide in the droplets in the emulsion.
  • nickel hydroxide is precipitated in the droplets in the emulsion
  • the emulsion is maintained as it is or it is destroyed, and then the nickel hydroxide is separated by, for example, centrifugation, washed and dried, thereby providing the desired fine particles of nickel hydroxide.
  • cobalt hydroxide or copper hydroxide is also the case with cobalt hydroxide or copper hydroxide.
  • the emulsion is subjected to aeration usually at a temperature of not more than 100°C under the normal pressure or the emulsion is subjected to suction under a reduced pressure to evaporate volatile components including ammonia from within the droplets in the emulsion, however, it is especially preferred that suction is applied to the emulsion with heating under a reduced pressure.
  • the temperature and pressure conditions are not specifically limited, but the pressure is usually under the atmospheric pressure, preferably under a reduced pressure (vacuum) of 400mmHg or less, while the limit of the reduced pressure (vacuum) may be about 5 mmHg, although depending on economy of operation.
  • the temperature may range from 0°C to 90°C, and preferably from 10 °C to 80°C, and most preferably 20°C to 70°C.
  • the emulsion may be simply stirred under the normal pressure to evaporate volatile components including ammonia from within the droplets of the solution of nickel salt in the emulsion.
  • air may be blown into the emulsion, i.e., the emulsion may be aerated under the normal pressure, if necessary with heating.
  • the thus formed carbonate or hydroxide is dried in the emulsion as described hereinbefore and separated by, for example, centrifugation, washed and dried, thereby providing the desired fine spherical particles of carbonate or hydroxide of nickel, cobalt or copper.
  • nickel carbonate While hitherto commonly available nickel carbonate, for example, are in the form of amorphous or non-spherical particles, a carbonate or a hydroxide of nickel, cobalt or copper is obtained as fine spherical particles according to the invention. Accordingly, such fine spherical particles are useful as themselves as a catalyst for use in organic synthesis, a carrier for use in a catalyst, a pigment, a filler or a glazes.
  • the aqueous solution of the nickel salt in which the surfactant was dissolved was mixed with the non-aqueous medium in which the surfactant was dissolved and the resulting mixture was stirred for 3 minutes using a homomixer (available from Tokushu Kika Kogyo K.K.) at 1500 rpm to prepare a W/O emulsion.
  • a homomixer available from Tokushu Kika Kogyo K.K.
  • Suction was applied to the emulsion under a reduced pressure of 20 to 30 mmHg at a temperature of 50°C and volatile components mainly comprising ammonia and carbon dioxide were evaporated to precipitate basic nickel carbonate in the droplets of the solution in the emulsion. Thereafter, further suction was applied to the emulsion under a reduce d pressure to evaporate volatile components mainly comprising water to dry the thus formed spherical particles of the nickel carbonate in the droplets.
  • Example 1 141 g of commercially available basic nickel carbonate and 331 g of ammonium hydrogencarbonate were added to 15% aqueous ammonia and stirred to prepare an aqueous ammonia-ammonium hydrogencarbonate solution of basic nickel carbonate (1.1 mol/L, in terms of Ni) having a pH of 9.5.
  • aqueous ammonia-ammonium hydrogencarbonate solution of basic nickel carbonate (1.1 mol/L, in terms of Ni) having a pH of 9.5.
  • spherical particles of basic nickel carbonate having a particle size of 0.1 to 5 ⁇ m and an average particle size of 1.3 ⁇ m were obtained.
  • Fig. 7 It was confirmed by an X-ray diffraction diagram shown in Fig. 7 that the obtained particles were composed of basic nickel carbonate.
  • Fig. 8 is a scanning electron micrograph of the particles of the basic nickel carbonate.
  • Fig. 9 is a scanning electron micrograph of the particles of the basic nickel carbonate.
  • Fig. 11 It was confirmed by an X-ray diffraction diagram shown in Fig. 11 that the obtained particles were composed of basic nickel carbonate.
  • Fig. 12 is a scanning electron micrograph of the particles of the basic nickel carbonate.
  • Fig. 15 It was confirmed by an X-ray diffraction diagram shown in Fig. 15 that the obtained particles were composed of nickel hydroxide.
  • Fig. 16 is a scanning electron micrograph of the particles of the nickel hydroxide.
  • the basic nickel carbonate thus formed was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 25 ⁇ m and an average particle size of 4.3 ⁇ m were obtained.
  • the basic nickel carbonate thus formed was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 13 ⁇ m and an average particle size of 3.0 ⁇ m were obtained.
  • the basic nickel carbonate thus formed was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 15 ⁇ m and an average particle size of 2.5 ⁇ m were obtained.
  • a W/O emulsion was prepared in the same manner as in Example 14.
  • the emulsion was stirred at a temperature of 70°C under the normal pressure to evaporate volatile components mainly comprising ammonia from within the droplets in the solution, thereby to precipitate basic nickel carbonate in the droplet in the emulsion.
  • the emulsion was further stirred and volatile components mainly comprising water were evaporated from within the droplets, thereby drying the particles of basic nickel carbonate thus formed in the emulsion.
  • the basic nickel carbonate was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 10 ⁇ m and an average particle size of 2.3 ⁇ m were obtained.
  • a W/O emulsion was prepared in the same manner as in Example 20.
  • the emulsion was stirred at a temperature of 70°C under the normal pressure to evaporate volatile components mainly comprising ammonia from within the droplets in the solution, thereby to precipitate nickel hydroxide in the droplet in the emulsion.
  • the emulsion was further stirred and volatile components mainly comprising water were evaporated from within the droplets, thereby drying the particles of nickel hydroxide thus formed in the droplets in the emulsion.
  • the nickel hydroxide thus obtained was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of nickel hydroxide having a particle size of 0.1 to 15 ⁇ m and an average particle size of 2.8 ⁇ m were obtained.
  • a W/O emulsion was prepared in the same manner as in Example 1. Suction was applied to the emulsion at a temperature of 50 °C under a reduced pressure of 100 mmHg to evaporate volatile components mainly comprising ammonia and carbon dioxide from within the droplets in the solution, thereby to precipitate basic nickel carbonate in the droplet in the emulsion. Then, the emulsion was further stirred and volatile components mainly comprising water were evaporated from within the droplets, thereby drying the particles of basic nickel carbonate thus formed in the droplets in the emulsion.
  • the basic nickel carbonate thus obtained was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 13 ⁇ m and an average particle size of 2.2 ⁇ m were obtained.
  • the basic nickel carbonate was centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 20 ⁇ m and an average particle size of 3.0 ⁇ m were obtained.
  • a W/O emulsion was prepared in the same manner as in Example 1. Suction was applied to the emulsion at a temperature of 50°C under a reduced pressure of 200 mmHg to evaporate volatile components mainly comprising ammonia and carbon dioxide from within the droplets in the solution, thereby to precipitate basic nickel carbonate in the droplets in the emulsion. Then, the emulsion was further stirred and volatile components mainly comprising water were evaporated from within the droplets, thereby drying the particles of basic nickel carbonate thus formed in the droplets in the emulsion.
  • a W/O emulsion was prepared in the same manner as in Example 1.
  • the emulsion was aerated at a temperature of 50°C under the normal pressure while being stirred to evaporate volatile components mainly comprising ammonia and carbon dioxide from within the droplets in the solution, thereby to precipitate basic nickel carbonate in the droplets in the emulsion.
  • the emulsion was further stirred and volatile components mainly comprising water were evaporated from within the droplets, thereby drying the particles of basic nickel carbonate thus formed in the droplets in the emulsion.
  • a W/O emulsion was prepared in the same manner as in Example 1. Nitric acid (2 mol/L) was added dropwise to the W/O emulsion over 3 hours to gradually neutralize the emulsion, thereby to precipitate basic nickel carbonate in the droplets in the emulsion. The precipitates were collected by filtration, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 15 ⁇ m and an average particle size of 1.5 ⁇ m.
  • a W/O emulsion was prepared in the same manner as in Example 2. Nitric acid (2 mol/L) was added dropwise to the W/O emulsion over 3 hours to gradually neutralize the emulsion, thereby to precipitate basic nickel carbonate in the droplets. The precipitates were collected by filtration, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 13 ⁇ m and an average particle size of 1.3 ⁇ m.
  • a W/O emulsion was prepared in the same manner as in Example 5. Nitric acid (2 mol/L) was added dropwise to the W/O emulsion over 3 hours to gradually neutralize the emulsion, thereby to precipitate basic nickel carbonate in the droplets. The precipitates were collected by filtration, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 20 ⁇ m and an average particle size of 1.8 ⁇ m.
  • a W/O emulsion was prepared in the same manner as in Example 14. Nitric acid (2 mol/L) was added dropwise to the W/O emulsion over 3 hours to gradually neutralize the emulsion, thereby to precipitate basic nickel carbonate in the droplets. The precipitates were collected by filtration, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of basic nickel carbonate having a particle size of 0.1 to 7 ⁇ m and an average particle size of 2.3 ⁇ m.
  • Fig. 19 is a scanning electron micrograph of the particles of the basic nickel carbonate.
  • a W/O emulsion was prepared in the same manner as in Example 20. Nitric acid (2 mol/L) was added dropwise to the W/O emulsion over 3 hours to gradually neutralize the emulsion, thereby to precipitate nickel hydroxide the droplets. The precipitates were collected by filtration, washed with hexane, methanol and water in this order, and dried at a temperature of 100°C for 2 hours, to provide spherical particles of nickel hydroxide having a particle size of 0.1 to 40 ⁇ m and an average particle size of 7.5 ⁇ m.
  • Fig. 21 is a scanning electron micrograph of the particles of the nickel hydroxide.
  • Fig. 23 is a scanning electron micrograph of the particles of the basic copper carbonate.
  • Fig. 25 It was confirmed by an X-ray diffraction diagram shown in Fig. 25 that the obtained particles were composed of basic cobalt carbonate.
  • Fig. 26 is a scanning electron micrograph of the particles of the basic cobalt carbonate.
  • a nonionic surfactant polyoxyethylene sorbitan monooleate having an HLB value of 15 (RHEODOL TW-0120, available from Kao Corp.) was added to 200g of the solutioN of nickel salt and stirred at 50°C to dissolve the surfactant in the solution.
  • 50 g of a nonionic surfactant, sorbitan monooleate having an HLB value of 4.3 (RHEODOL SP-010, available from Kao Corp.) were added at a temperature of 80°C to 800 g of a non-aqueous medium, squalan (Super Squalane, available from K.K. Squatech) having a boiling point of about 280°C to dissolve the surfactant in the non-aqueous medium.
  • the aqueous solution of the nickel salt in which the surfactant was dissolved was mixed with the non-aqueous medium in which the surfactant was dissolved and the resulting mixture was stirred for 5 minutes using a homomixer (available from Tokushu Kika Kogyo K.K.) at 5000 rpm twice to prepare a W/O emulsion.
  • a homomixer available from Tokushu Kika Kogyo K.K.
  • Suction was applied to the emulsion under a reduced pressure of 20 to 30 mmHg at a temperature of 50°C and volatile components mainly comprising ammonia and carbon dioxide were evaporated to precipitate basic nickel carbonate in the droplets of the solution in the emulsion. Thereafter, further suction was applied to the emulsion under a reduced pressure to evaporate volatile components mainly comprising water to dry the spherical particles of the nickel carbonate in the emulsion.
  • Fig. 27 is a particle size distribution diagram of the particles of the basic nickel carbonate thus obtained.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
EP99921191A 1998-05-21 1999-05-19 Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre Expired - Lifetime EP1013610B1 (fr)

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JP13968398 1998-05-21
JP13968398 1998-05-21
JP35418898A JP4174887B2 (ja) 1998-05-21 1998-12-14 ニッケル、コバルト又は銅の炭酸塩又は水酸化物の微細な球状の粒子の製造方法
JP35418898 1998-12-14
PCT/JP1999/002634 WO1999059921A1 (fr) 1998-05-21 1999-05-19 Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre

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EP3251740A4 (fr) * 2015-01-26 2018-09-26 Miyazaki Prefecture Procédé de production de dispersion de nanoparticules dans l'huile

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Publication number Priority date Publication date Assignee Title
EP1826181A1 (fr) * 2004-10-27 2007-08-29 Sumitomo Chemical Company, Limited Poudre d'hydroxyde de nickel et méthode de fabrication de ladite poudre
EP1826181A4 (fr) * 2004-10-27 2010-09-22 Sumitomo Chemical Co Poudre d'hydroxyde de nickel et méthode de fabrication de ladite poudre
US8147783B2 (en) 2004-10-27 2012-04-03 Sumitomo Chemical Company, Limited Nickel hydroxide powder and method for producing same
EP3251740A4 (fr) * 2015-01-26 2018-09-26 Miyazaki Prefecture Procédé de production de dispersion de nanoparticules dans l'huile
US10441935B2 (en) 2015-01-26 2019-10-15 Miyazaki Prefecture Method of producing nanoparticle-in-oil dispersion

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WO1999059921A1 (fr) 1999-11-25
EP1013610A4 (fr) 2001-08-16
EP1013610B1 (fr) 2003-09-24
DE69911559T2 (de) 2004-08-05
JP2000044252A (ja) 2000-02-15
CN1274335A (zh) 2000-11-22
US6197273B1 (en) 2001-03-06
DE69911559D1 (de) 2003-10-30
KR100618071B1 (ko) 2006-08-30
KR20010022049A (ko) 2001-03-15
CN1115301C (zh) 2003-07-23

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